Charles Constable, the BBC's acting controller of distribution, becomes five's director of strategy, while the marketing director's role is filled by Jane Scott, who was the corporation's controller of TV marketing, strategy and channel development.
The two appointments follow five's decision to split the strategy and marketing functions. David Pullan had held both jobs before becoming FHM Worldwide's managing director almost a year ago.
Scott, who has held senior marketing roles at the Financial Times and The Daily Telegraph, was thought to have been a contender for the top marketing post at the BBC. However, the job went to Tim Davie, PepsiCo Europe's former marketing chief.
Constable, who joined the BBC from Granada Media in 2001, takes on the task of defending five's audience share as the number of channels multiplies.
Jane Lighting, five's chief executive, said: "I'm delighted we have been able to attract someone of Charles' tremendous ability and experience."